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By John J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. * * * * In the early days, the process was thought of as a simple one. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried.

Jan 4, 1958

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature1135°C. (2095°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm, at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By William L. Russell

A new instrument for measuring bulk and grain vol-urnes is described, and compared in accuracy with two modifications of Nutting's method, All three methods are reasonably fast, and in all three the probable error in the determinations of bulk volume can be kept down to about 0.1 to 0.2 per cent. INTRODUCTION The new pycnometer described in this paper is designed to give speed without sacrificing accuracy. Some time ago Russell1 described a somewhat similar appa-ratus; however, the instrument described in the present paper is more accurate. Nutting' designed the pycnom-eter shown in Fig. 1 (A and B), and Pirson3 has shown points like those of Fig. 1-D. The procedure described in this paper for using Nutting's pycnometer has been modified from that used by Nutting. CHOICE OF LIQUIDS The best liquids for measuring grain volumes are hydrocarbons or chlorinated hydrocarbons which evaporate slowly. Trimethylbenzene or mesitylene, triethylben-zene, carbon tetrachloride, and tertalin have been used for this purpose. Any of these liquids or mercury may be used for measuring bulk volume. PREVENTING ERRORS DUE TO INVASION OF LIQUID Errors due to the invasion of the porous, permeable bulk samples by the liquid of measurement may be prevented or greatly reduced by using mercury, by applying an impervious coating, or by soaking the bulk samples in the liquid of measurement until bubbles cease issuing from them. Errors are produced only by the invasion of the samples which occurs between movement when the samples are weighed in air and the moment the weight of liquid displaced by the sample in the pycnometer is determined. No error is produced by varying degrees of filling of the pore space of the samples by the liquid of measurement. The excess liquid should be wiped from the samples immediately before the weight in air W1, is determined, and they should be placed in the pycnometers immediately. OPERATION OF NEW INSTRUMENT The new pycnometer is shown in Fig. 2. It consists of two glass parts which fit together at a ground glass joint. The spaces J and D are connected by fine glass tubes E, and the space J must be larger than the space D by at least the volume of the largest sample to be tested. The projections H afford a grip for twisting when the two parts tend to stick together. The position of the sample in mercury is shown by I, and in other liquids by M. F is a permanent mark on the glass, and G is a tem-Some marker. In order to determine the position at which G should be placed, invert the instrument so that A is at the bottom, and fill space D. Place the cub K

Jan 1, 1958

By H. J. Snyder

Both the room-temperature and 600°F (315°C) primary solid-solution phase boundaries for the silver comer of the Ag-Cd-In temary system have been determined using X-ray diffraction and metallo-graphic techniques. Solid solubility of indium in silver at room temperature and 600°F (315°C) is shown to be between 20.3 and 21.7 wt pct, and corrects the previously extrapolated value of 18 wt pct appearing in the literature. The solid solubility of cadmium in silver at room temperature, not previously established, is shown to be between 34.9 and 41.3 wt pct. The solid solubility of cadmium in silver at 600°F (315°C) is confirmed as 43.2 wt pct. The shape of the primary phase boundary line for the subject temary system appears straight at room temperature and curves con-vexly towards the solvent (silver) comer at 600°F (315°C). THIS investigation was undertaken to initiate development of the Ag-Cd-In ternary diagram by establishing the primary solid-solution phase boundary in the silver corner of the diagram. At the present time, a diagram for this ternary system is not available, while this system appears to offer potential for a variety of uses. One alloy in the system has already proven to be useful as a control rod material in nuclear reactors.1"3 To encourage additional exploration of the potential of the system an understanding of its ternary diagram would be beneficial. It is towards this end that the present study is directed. LITERATURE SURVEY In undertaking this study, a comprehensive literature survey was first conducted to find information that would be useful for guidance. Useful knowledge did result from investigating the respective solubilities of indium and cadmium in silver as indicated in the binary constitutional diagrams of the systems Ag-In and Ag-Cd and also reviewing possible shapes of ternary primary phase boundaries. Weibke and Eggers~ used metallographic techniques to establish the system In-Ag as illustrated in Fig. Is This diagram shows that silver in the solid state is capable of dissolving approximately 18 wt pct In. This solid solubility of indium in silver holds true from room temperature up to 1276°F (691°C), then decreases continuously up to 1'761°F (960.5"C), the melting point of the silver. The solid-solubility limit of indium in silver established by Weibke and Eggers has been confirmed by Hume-Rothery and Reyno1ds. G Durrant' used a method which consisted of microscopic examination of quenched specimens to establish the Cd-Ag system as displayed in Fig. 2.' The primary phase boundary of Fig. 2 proved to be in good agreement (ie., within 1 wt pct) with other studies*'1' of the Ag-Cd system made using X-rays and metallog-

Jan 1, 1968

By William M. Shakespeare

Thin sheet copper in wide widths and long lengths is being made electrolytically on a commercial scale at the Raritan Copper Works, Perth Amboy, N. J. This achievement is the result of three years of intensive development preceded by almost ten years of intermittent research. While the idea of producing sheet copper by the electrolytic process is old, the literature on the subject is limited. It is evident, however, that the idea has been attractive to many investigators for years, if the issued patents in the field may be taken as an indication. These patents may be divided into three groups. In one group metal is deposited on some form of endless cathode, of which a revolving cylinder or drum is the most common. The cathode moves slowly and at such a rate that metal of the desired thickness is deposited during one pass through the electrolyte. The deposited metal is stripped off the cathode at a point above the solution level and, after washing and drying, is wound up immediately. In the next group of patents a band of thin metal is increased in thickness by being guided through an electrolytic tank in opposition to suitable anodes. The third group covers means of producing sheets of definite dimensions where flat plates or revolving cylinders are used as cathodes. With such cathodes, sheets of definite dimensions are built up to the desired thickness and then stripped off. The process as worked out at the Raritan Copper Works combines the methods of the first two groups. In the first stage a sheet weighing 1 oz. to the square foot is produced on a revolving cylinder. This sheet is increased to any desired thickness in the second stage. In the first stage (Fig. 1) a lead-covered copper drum is mounted horizontally on a lead-lined concrete tank so that it. is partly immersed in the electrolyte. The cylindrical surface of the drum immersed in the electrolyte is opposed by lead anodes spaced about 36 in. from it. The electrolyte, made up of appropriate quantities of copper and sulfuric acid, flows into and out of the tank continuously. The ebullition of gas at the surface of the anodes induces a vigorous circulation of electrolyte between the anodes and the drum surface, which is augmented by means of compressed air introduced through a pipe between the ends of the anodes under the center of the drum, not indicated on the diagram. This

Jan 1, 1934

By Roland J. Lapee

A history of the progress made in copper refining in Montana is presented. The casting furnaces and the newly rebuilt electrolytic refinery are descmbed and operating details are given. Experiences with various addition agents, effects of rernoval of chlorine from the electrolyte, and effects of separan on electrolyte and on copper deposit are discussed. Observatzons are made on the effect of various impurities in anode copper and behavior of thezr salts in electrolyte and in slime, on treatment of slime for removal of copper, and on electrolyte puriification problems. The improved method for production of starting sheets is described. Attention is given to new materials for construction and to improvement in matrials handling ad quality control. COPPER refining at Great Falls, Montana, dates back to 1892. The original plant produced 65,000 lb. of cathodes per day at a current density of 16 amp per sq ft. In this plant anodes and cathodes were handled to and from the cells by means of hand-operated chain blocks and were moved about the plant by hand trucks. Cathodes were melted in coal-fired, reverbera-tory furnaces, were charged by hand, and refined copper was dipped by hand and cast in iron molds. In 1916, a new, modern plant with capacity to refine 18 million Ib. copper per month was built. Two refining furnaces were built, and each was provided with a twenty-mold Clark casting wheel. In 1922, the furnaces were converted to the use of pulverized coal: in 1923, to the use of oil; and in 1928, to the use of natural gas. In 1926, the plant was enlarged 50 pct. The use of pulverized coal for refining copper at Great Falls was discussed1 in a paper presented at the Salt Lake City meeting of the Institute in September 1925. Also, a comparison of the use of various fuels in copper refining furnaces was discussed 2 in a paper presented at the New York meeting of the Institute in February 1932. Prior to 1943 the cellroom was operated with twenty-five 720-lb. anodes and 26 cathodes per cell. Four cathodes, each weighing about 165 lb., were produced from an anode. In 1943 the weight of the anode was reduced to 460 lb., and two cathodes, each weighing about 190 lb., were produced from an anode. In 1949, a Billet Casting Wheel for the production of 3 in. diam phosphor deoxidized billets was built. A paper, presented at the New York Meeting of the Institute in February 1956, describes3 this plant and operation. In the electrolytic refinery, production is controlled by variation of the current density. In 1956, germanium rectifiers on a separate electrical circuit were provided for the starting sheet section so that current density could be maintained at any desired figure. Also in 1956, a program of modernization and enlargement of the Electrolytic Copper Refinery was started. This program, when completed, will raise the capacity of the Great Falls Electrolytic Copper Refinery approximately 33 pct, to 33 million lb. of cathodes per month. Furnace capacity for melting cathodes and anode scrap is ample to take care of the increased production from the electrolytic refinery. This fortunate condition came about primarily as the result of the three following changes: 1) The furnaces were lengthened 10 ft in 1922 when the fireboxes were found unnecessary for burning powdered coal. 2) Furnace life, and hence furnace capacity, was increased by the successful efforts of the Copper Refinery staff to develop a method for sanding furnace side walls and roof. 3) The natural gas being used has a very low sulfur content. As a result, it is possible to reduce time spent rabbling and poling and thus greatly increase tons per furnace charge. TANKHOUSE AND TANKS The Great Falls Electrolytic Refinery is 535 ft long by 252 ft wide. The cells are arranged in four crane bays in which are operated seven 10 ton Whiting Cranes. The old cells are in groups of ten, with circulation of electrolyte through five cells in cascade and with aisles between the groups of ten cells. The new cells are nested in groups of sixteen with no aisles, are all on one level, and have individual circulation to each cell. Present plans call for 1792 commercial cells and 128 stripper cells. To reduce confusion during the construction period, and to use the cranes, cars, and other equipment already on hand, the cells in the rebuilt section were designed to have approximately the same inside dimensions as the cells in the old part of the

Jan 1, 1962

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970

By C. D. Woodward

The Anaconda Copper Mining Co. purchases 25,000 kw. of electric power for its mining operations at Butte, Mont. This power is delivered, over duplicate feeders, in the form of 60-cycle, 2400-volt, three-phase current, to five compressor plants, where most of the energy is used for driving air compressors. At the compressor plants are located the switching apparatus for controlling the 2400-volt power and distributing it to the various mines. At these points, also, there are a number of motor-generator sets for converting the alternating current to 275-volt direct current for the haulage systems. Pole lines convey the powcr from the compressor plants to outdoor transformer substations at most of the mines. When it is not economical to distribute the power at the lower voltages in the mines, transformers and motor-generator sets are placed at strategic points underground. All power is purchased on a maximum-demand basis; therefore there is installed at one of the compressor plants an eight-element totalizing graphic wattmeter. This instrument records simultaneously the value of all power taken at the numerous points of delivery, which not only climinates the diversity factor but permits load dispatching between compressor and pumping plants, and thus materially reduces the maximum demand from the power system. As most of the mine hoisting is done by 90-lb. compressed-air winding engines, the air-compressor equipment for the winding engines and mining operations is quite extensive. The standard air compressor has a rating of 7500 cu. ft. per min. of free air, and most of the compressors are directly connected to synchronous motors. The synchronous motors are designed for 80 per cent. loading power factor, thus facilitating power-factor correction of total mine load. Consequently by cooperation with the power company, the voltage of the power received at the compressor plants is constant. In the mines there are installed an induction motor load of approxi-mately 10,000 hp., and 4500 kv.-a,, in transformer capacity. It is the practice to install 2200-volt motors in the mincs, except those rated below 50 hp, hence there are in operation underground about 5000 hp., in the

Jan 1, 1923

By C. D. Woodward

The Anaconda Copper Mining Co. purchases 25,000 kw. of electric power for its mining operations at Butte, Mont. This power is delivered, over duplicate feeders, in the form of 60-cycle, 2400-volt, three-phase current, to five compressor plants, where most of the energy is used for driving air compressors. At the compressor plants are located the switching apparatus for controlling the 2400-volt power and distributing it to the various mines. At these points, also, there are a number of motor-generator sets for converting the alternating current to 275-volt direct current for the haulage systems. Pole lines convey the powcr from the compressor plants to outdoor transformer substations at most of the mines. When it is not economical to distribute the power at the lower voltages in the mines, transformers and motor-generator sets are placed at strategic points underground. All power is purchased on a maximum-demand basis; therefore there is installed at one of the compressor plants an eight-element totalizing graphic wattmeter. This instrument records simultaneously the value of all power taken at the numerous points of delivery, which not only climinates the diversity factor but permits load dispatching between compressor and pumping plants, and thus materially reduces the maximum demand from the power system. As most of the mine hoisting is done by 90-lb. compressed-air winding engines, the air-compressor equipment for the winding engines and mining operations is quite extensive. The standard air compressor has a rating of 7500 cu. ft. per min. of free air, and most of the compressors are directly connected to synchronous motors. The synchronous motors are designed for 80 per cent. loading power factor, thus facilitating power-factor correction of total mine load. Consequently by cooperation with the power company, the voltage of the power received at the compressor plants is constant. In the mines there are installed an induction motor load of approxi-mately 10,000 hp., and 4500 kv.-a,, in transformer capacity. It is the practice to install 2200-volt motors in the mincs, except those rated below 50 hp, hence there are in operation underground about 5000 hp., in the

Jan 1, 1923

By Arthur F. Wendt

In the manufacture of charcoal-blooms, washing or cleansing of the ore from adhering gangue has been practiced for many years. A sluice-box is even to-day used for that purpose in the Southern Appalachian Mountains. For the Lake Champlain bloomaries hard magnetic ores are crushed with stamps and then sluiced or jigged in hand-jigs. The stamps used in the Lake Champlain region are of the most primitive kind. They consist of a trip-hammer, dropping on a perforated cast-iron plate, through which the crushed ore escapes. Only friable rock can thus be successfully treated. To render the raw ore friable, a calcining or burning in piles on a bed of cordwood is resorted to. An expense of 35 cents per ton of crude rock treated is thus incurred. The crushed ore is shovelled or otherwise fed into jigs without previous sizing, except such as is incidental to crushing through the perforated bottom of the stamping-machine. In jigging this ore, it is allowed to pass through the bedding into the "hutch." The tailings are scraped off and wasted. They contain a large percentage of fine ore. In many instances, this is regained by subsequent sluicing. Such was the condition of the industry, when the writer's attention was first called to it in 1882. No attempt had been made to introduce into thiS branch of ore-dressing the notable improvements adopted in concentrating the ores of other metals. The result of the writer's investigations was the building in 1882 of the "Crown Point Separator." At the Crown Point Mines, N. Y., lean ore unfit for the blastfurnace (containing less than 331/3 per cent. of iron), was concentrated and used in the bloomary connected with the mines. The ore was burned here as elsewhere, and treated as described. The plant designed by the writer for Crown Point, is nearly a counterpart of that since erected by Messrs. Copeland and Bacon, contractors, for the Theal mine, Putnam County, New York, which is illustrated by the accompanying plate. The only difference is in

Jan 1, 1885

By Nigel B. Pearson

INTRODUCTION Chingola Division of Nchanga Consolidated Copper Mines Limited is situated in the Copper- belt of Zambia, approximately 30 kilometres south of the border with Zaire. It is the country's leading producer of copper and its principal foreign exchange earner, and has been, in its time, the largest single copper producer in the British Commonwealth and the second largest in the world. There are two 'primary' copper sources at the Division, namely Underground producing approximately 100 000 tonnes of contained copper annually, and the Open Pits, producing approximately 200 000 tonnes annually. Following the commissioning of the Tailings Leach Plant in 1974, treating final tailings, metallurgical recovery increased from approximately 70% to in excess of 80%. Extensive deposits of cobalt are present and following the rise in the market price in 1979 and 1980, plans were made to extract this separately. Cobalt production commenced in 1980 from Underground and will increase substantially when the Open Pit cobalt reserves become available in approximately 2 years time. This paper covers the development of the production method of the principal Underground Orebody, known as the Lower Orebody, and the control systems applied to it. HISTORY The Lower Orebody, formerly known as the Nchanga West Orebody, was discovered by extensive Diamond Drilling operations in the late 1920's. Development of the Shaft complex and the orebody commenced and continued until 1931 when flooding from development on the 480 foot horizon necessitated closure. The mine remained closed until 1937 and production commenced from the Lower Orebody in 1939. Various expansion schemes of the Metallurgical Plants and the Underground workings were completed over the years with the result that Underground production increased steadily to in excess of 150 000 tonnes copper annually in the 1960's. In recent years production has levelled out at slightly less than 100 000 tonnes annually. This decrease is as a result of producing from a lower grade reserve, available within a more limited production front, and the application of production constraints in the light of experience gained. GEOLOGY Within the Nchanga Mining Licence Area of Chingola Division, there are a total of 14 known copper orebodies in the basal part of a thick succession of sediments of Pre-Cambrian age. The sediments rest on a Basement Complex of granites, gneisses and schists. Three superimposed stratiform orebodies, known locally as the Lower, Intermediate and Upper Orebodies, occur over a vertical interval of approximately 150m. Current annual copper production is approximately 300 000 tonnes. The ore originates from four different mining operations, one Underground mine and three Open Pits. Approximately 9 million tonnes of ore grading between 3 and 3.5% copper are milled annually. The two largest sources of ore, the Under- ground mine and the Nchanga Open Pit are on the gently dipping south limb of the Nchanga Syncline (Figure 1). In the Nchanga Open Pit the major source of ore is the Upper Orebody with lesser tonnages from the Intermediate and Lower Orebodies. In the Underground mine the Lower Orebody is the only orebody being mined, underground mining of the Upper Orebody being suspended for economic reasons in 1978. The typical stratigraphic column is illust- rated in the legend on Figure 1. The footwall rocks comprise either Nchanga Red Granite or the Arkose formation, both of which are hard competent rocks, offering generally good mining conditions for footwall development. Copper mineralisation of the Lower Orebody extends from the upper part of the Arkose to the top of the Lower Banded Shales. Overlying the Arkose is the Transition zone (0-18111 in thickness). The Transition zone comprise a lower member, Transitional Arkose, consisting of incoherent kaolinised sandstone, and an upper member, Transitional Lower Banded Shales consisting of normally soft bleached and silicified shale. The soft nature of the Transitional rocks is

Jan 1, 1981

By M. N. Short, I. A. Ettlinger

M. N. Short,? Washington, D. C., and I. A. Ettlinger, New York', N. Y. (New York Meeting. February, 1926) The Pioneer mining district, better known as the Superior district, from its principal town, is located in Pinal County in south-central Arizona about 80 miles east of Phoenix and 22 miles west of Miami. The region embraces a, confused series of mountain ranges of moderate height but precipitous slopes, between which lie irregular valleys filled with alluvial detritus. The average elevation is about 2800 ft. in the valleys and the summits of the ranges reach 2000 ft. above this. Superior is situated on the north bank of Queen Creek where it emerges from one of those ranges into a more or less basin-shaped valley. The drainage of Queen Creek is to the southwest and the flood waters spread out and lose themselves in the desert northeast of Florence, the county seat of Pinal County. The Magma copper mine (Fig. 1) is the only producer in the district. Although discovered in 1875, its production has been important only

Jan 1, 1927

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do's or the H'S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.' In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,' the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.' Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.' The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.'' Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

By H. E. Swanson

A description of the field apparatus has been published by D. G. Brubaker. Data from laboratory model studies of the in-line and broadside methods of operation are detailed. The conductor models include a single sheet conductor at several strike and dip angles and a schistose-type conductor. In addition, data on the effects of the strike length and of the depth of the conductor are presented for the broadside method of operation. All of the data show that the inclintion reverses direction over the top edge of dipping single sheet conductors. Differences between anomalies over conductors dipping between 90" and 30" are subtle,but flat-lying sheets can be readily distinguished from steeply dipping sheets. Schistose conductors are easily distinguished from single sheet conductors, and a procedure is given for determing the direction of schistosity. The depth of penetration under ideal conditions is 0.7 of the coil separation. In 1950, The New Jersey Zinc Co. (of Pa.) developed a lightweight apparatus for electromagnetic prospecting. A description of this apparatus has been published by D. G. Brubaker.1 It consists of a small, battery-powered vertical source coil and a direction-finding receiving coil. Source and receiver are kept a fixed distance apart and move as a unit along the survey lines. At each receiver station the inclination of the magnetic field created by the source is measured. Two methods of operation are used, in each of which measurements are taken with a constant source-to-receiver distance and with the plane of the source oriented to pass through the receiver station. In one procedure, called the in-line method, source and receiver travel in tandem along the same line. In the other procedure, called the broadside method, source and receiver move along adjacent lines, with the source-to-receiver direction oriented parallel to the assumed strike direction. The data recorded in either case are the inclinations, measured in degrees from the horizontal, of the magnetic field created by the source. These data are plotted at the receiver stations on a map. Scale-model studies of both methods of operation have been conducted in the laboratory and are reported in this paper. APPARATUS Small source and receiving coils wound with many turns of fine copper wire were used to produce and measure an alternating magnetic field in the same manner as the field apparatus. The model source coil was mounted in a vertical position and oriented so that the receiving coil was in the plane of the source. The receiving coil was mounted in a frame so it could be rotated to obtain the inclination measurements. The source coil was excited by a 100-kc signal generator. A tuned amplifier and a voltmeter were used to detect the null position of the receiving coil. The coils used in the field apparatus are usually spaced about 400 ft. The coils used in the model work were spaced from 4 in. to 4 ft apart. Thus the scale of the model work ranges between 1/1200 to 1/100 natural size. The model conductors were aluminum-coated building paper supported on wooden frames. The conductivity-thickness product was measured using a four-electrode system and was found to be about 300 ohms-'. CONDUCTIVITY CONSIDERATIONS The electromagnetic response from a thin sheet conductor is a function of the product of the conductivity of the sheet times the thickness of the sheet times the frequency of the alternating electromagnetic field times some linear dimension of the system such as the coil separation which indicates scale. The secondary electromagnetic field produced by the conductor increases in amplitude from zero at zero conductivity to a maximum value for infinite conductivity, while the phase of the secondary field with respect to the primary field shifts from 90" at zero conductivity to 0" at infinite conductivity. Several authors2-' have shown that most of both the increase in amplitude and the change in phase of the secondary field takes place over a three-decade range of the conductivity-thickness-frequency product. Only small changes in the amplitude and

Jan 1, 1961

By E. R. Buchanan, R. E. Reed-Hill

A transmission electron microscope study was made of magnesium single crystals deformed in torsion using the basal pole as the forsional axis. While this type of deformation is predicted to result in the formation of hexagonal networks of screw dislocations, these networks were not observed. The basic dislocation arrangement consisted of arrays of nearly parallel and approximately equally spaced dislocations. The average dislocation density was over an order of magnitude higher than that required to account for the torsional deformation. The observed high rate of work hardening in these crystals is consistent with both their high dislocation densities and the arrangement of dislocations in pile-ups. The experimental observations are also in agreement with the assumption that dislocation sources are activated not only at the surface but at interior locations as well. In considering torsional deformation, Amelinckx and Dekeyser1 postulated that when a torque is applied to a crystal oriented with a glide plane normal to the specimen axis, deformation occurs by the following steps: 1) Nucleation of dislocation sources at or near the specimen surface in areas where the shear stress, resolved along a slip Burgers vector, is a maximum; 2) the screw orientations of the dislocations accommodating the twist move inwards towards the specimen center. If two glide directions lie on the glide plane, the geometry shown in Fig. 1 should result; 3) the screw dislocations that pile up in the central part of the specimen cross-slip to form a grid. At the same time, screws of opposite sign and most edges leave the specimen. Tinder,2 using zinc crystals twisted about the basal pole, independently reached essentially the same conclusions. He suggested a mechanism involving nucleation of ?(1120) screw dislocations at the six points of highest resolved shear stress that lie on the cross-section near the surface. Under the applied shear stress these dislocations were assumed to move inward and interact so as to form a hexagonal network of screw dislocations. Today it is often accepted that rotational slip occurs by a mechanism of the above type, but to our understanding this has never been experimentally proved. This paper reports an experimental study of rotational slip, using magnesium single crystals, that indicates that in this metal rotational slip does not conform well to this mechanism. EXPERIMENTAL PROCEDURES Mechanical Testing. Specimens with a (0002) axis were prepared from magnesium crystals of 99.95 pct purity grown by Jillson's3 modified Bridgman technique. The crystals were acid machined into cylindri-

Jan 1, 1970

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

By Norman Brown

It is suggested that the difference in ease of cross-slip among the fcc metals determines the relative amounts of [111] and [100] wire texture which occur in each metal. Since the ease of cross-slip is controlled by the stacking fault energy, it turns out that the amount of [111] texture should increase as the stacking fault energy increases. Arguments and existing data are presented to support the above suggestion. THE fcc metals generally have a dual texture, [11 and [loo], after wire drawing. As yet no fundament explanation exists concerning the variation of the amounts of each texture among the metals. Barrett&apos; has compiled data which show how the relative amounts of each texture vary from 100 pct [Ill] in the case of aluminum to 25 pct [l1] for silver. In this paper it is suggested that the value of stacking fault energy plays a major part in determining the amount of each type of texture. The double texture has its origin in the classical rotation of a single crystal under tension. An equilibrium position of the crystal is one in which three or more equivalent slip systems are operating simu taneously. Most crystals, initially, tend to rotate toward the [1ll] or the [l00] pole depending upon its initial orientation. This single-crystal behavior is essentially the same as the rotational behavior of the polycrystalline metal as worked out by Taylor.2 The next point to consider is whether the [Ill] or [100] orientation is more stable. There have been many discussions of this question3&apos;" which, in general, have lead to the conclusion that 11111 is most stable. For example, Pickus and Mathewson 4 suggested that a [Ill] texture produces more effective flow becake the [ 110] slip direction makes a smaller angle with the [111] than with the [loo]. A crude statistical argument will be presented which again favors the (1111 orientation. In order to maintain a pure [loo] wire texure, slip must occur in equal proportions in four of the six possible <110>slip directions. In order to maintain a pure [Ill] texture, slip must occur in equal proportions in only three of the six <110>directions. Since the <110> directions are the only slip directions in a fcc metal and if it is assumed that each of these six directions is equally probable, then the relative probability of a [1ll] texture vs a [l00] texture may be calculated. The statistical weight of a particular texture is the multiplicity of a texture times the probability of obtaining any one. The statistical weight for [Ill] is

Jan 1, 1962

By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world&apos;s cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976